US6022933A - Process for the preparation of polyethylene - Google Patents

Process for the preparation of polyethylene Download PDF

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Publication number
US6022933A
US6022933A US08/911,263 US91126397A US6022933A US 6022933 A US6022933 A US 6022933A US 91126397 A US91126397 A US 91126397A US 6022933 A US6022933 A US 6022933A
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United States
Prior art keywords
range
ethylene
reactor
recycle gas
weight
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Expired - Lifetime
Application number
US08/911,263
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English (en)
Inventor
Dale Andrew Wright
Theodore Randolph Engelmann
Antonios Nicholas
Francois Alexandre
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Petromont and Co Ltd
Univation Technologies LLC
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Petromont and Co Ltd
Union Carbide Chemicals and Plastics Technology LLC
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Application filed by Petromont and Co Ltd, Union Carbide Chemicals and Plastics Technology LLC filed Critical Petromont and Co Ltd
Priority to US08/911,263 priority Critical patent/US6022933A/en
Assigned to PETROMONT AND COMPANY, LIMITED reassignment PETROMONT AND COMPANY, LIMITED ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ALEXANDRE, FRANCOIS
Priority to ZA986046A priority patent/ZA986046B/xx
Priority to ARP980103910A priority patent/AR016807A1/es
Priority to PT98940884T priority patent/PT1003792E/pt
Priority to AT98940884T priority patent/ATE210157T1/de
Priority to KR1020007001467A priority patent/KR20010022865A/ko
Priority to PCT/US1998/016851 priority patent/WO1999009075A1/en
Priority to PL98338556A priority patent/PL338556A1/xx
Priority to DE69802812T priority patent/DE69802812T2/de
Priority to ES98940884T priority patent/ES2165186T3/es
Priority to CN98810070A priority patent/CN1275136A/zh
Priority to RU2000106041/04A priority patent/RU2184743C2/ru
Priority to TR2000/00338T priority patent/TR200000338T2/xx
Priority to EP98940884A priority patent/EP1003792B1/en
Priority to CZ20000521A priority patent/CZ299738B6/cs
Assigned to UNION CARBIDE CHEMICALS & PLASTICS TECHNOLOGY CORPORATION reassignment UNION CARBIDE CHEMICALS & PLASTICS TECHNOLOGY CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: WRIGHT, DALE ANDREW, ENGELMANN, THEODORE RANDOLPH, NICHOLAS, ANTONIOS
Assigned to UNION CARBIDE CHEMICALS & PLASTICS TECHNOLOGY CORPORATION reassignment UNION CARBIDE CHEMICALS & PLASTICS TECHNOLOGY CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: WRIGHT, DALE ANDREW, ENGELMANN, THEODORE RANDOLPH, NICHOLAS, ANTONIOS
Publication of US6022933A publication Critical patent/US6022933A/en
Application granted granted Critical
Priority to BG104160A priority patent/BG104160A/xx
Assigned to UNION CARBIDE CHEMICALS & PLASTIC TECHNOLOGY CORPORATION reassignment UNION CARBIDE CHEMICALS & PLASTIC TECHNOLOGY CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: PETROMONT AND COMPANY, LIMITED NOW KNOWN AS PETROMONT AND COMPANY, LIMITED PARTNERSHIP
Assigned to UNIVATION TECHNOLOGIES, LLC reassignment UNIVATION TECHNOLOGIES, LLC ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: UNION CARBIDE CHEMICALS & PLASTICS TECHNOLOGY CORPORATION
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/02—Ethene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/1809—Controlling processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/34—Polymerisation in gaseous state
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/901—Monomer polymerized in vapor state in presence of transition metal containing catalyst
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/905—Polymerization in presence of transition metal containing catalyst in presence of hydrogen

Definitions

  • This invention relates to a process for preparing a high density polyethylene, which is particularly useful in pipe, molding, and geomembrane applications.
  • High density polyethylene which spans a density range from 0.940 to 0.958 gram per cubic centimeter, finds application in injection molding, rotational molding, sheet, tubing, hose, and, of particular interest here, pipe, blow molding and geomembranes.
  • HDPE products for pipe, blow molding and geomembranes should exhibit high resistance to slow crack growth in order to prevent or significantly delay the occurrence of brittle failures under stress.
  • PENT Pennsylvania Notch Tensile
  • the PENT test was developed in an effort to simulate the slow crack growth resistance of a resin or fabricated pipe in an accelerated manner.
  • the PENT test has been approved as ASTM-F 1473 and is widely used in the pipe industry as a quality control 1 quality assurance tool for the production of pressure rated pipe.
  • the HDPE should have consistently good extrusion processability.
  • An object of this invention is to provide HDPE resins which exhibit high resistance to slow crack growth when converted to pipe, molded articles, geomembranes, or other products, and have a high level of processability.
  • the process is one for preparing high density polyethylene in the gas phase comprising contacting a mixture comprising ethylene and one or more alpha-olefins with the supported reaction product of a bis-hydrocarbylsilyl chromate and a hydrocarbylaluminum compound or a hydrocarbyl boron compound in a fluidized bed reactor having a recycle gas line, under polymerization conditions, with the following provisos:
  • the atomic ratio of aluminum to chromium is in the range of about 0.1:1 to about 2.9:1;
  • the amount of catalyst is in the range of about 0.005 to about 0.25 part by weight based on 100 parts by weight of the high density polyethylene;
  • the partial pressure of ethylene is in the range of about 200 to about 400 psia;
  • oxygen and/or another catalyst poison is introduced into the reactor in the range of about 0.005 to about 0.5 part by volume of catalyst poison per million parts by volume of ethylene;
  • hydrogen is introduced into the reactor in the range of about 0.005 to about 0.5 mole of hydrogen per mole of ethylene;
  • the polymerization is carried out at a temperature in the range of about 80 to about 110 degrees C.
  • a relatively low boiling inert hydrocarbon is introduced into the recycle gas line where it raises the dew point of the recycle gas, which is comprised of alpha-olefins and other reactor gases, and the recycle gas is partially condensed and recycled to the reactor where it promotes cooling by evaporation.
  • HDPE is a copolymer of ethylene and one or more alpha-olefins.
  • the alpha-olefin can have 3 to 12 carbon atoms, and preferably has 3 to 8 carbon atoms.
  • Examples of the alpha-olefins are propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, and 1-octene.
  • One or two alpha-olefins are preferred.
  • the most preferred alpha-olefin is 1-hexene.
  • the total amount of alpha-olefin in the copolymer can be about 0.1 to about 3 parts by weight based on 100 parts by weight of the copolymer, and is preferably about 0.5 to about 2.5 parts by weight.
  • the resin can have a melt index (I 2 ) in the range of about 0.01 to about 0.5 gram per 10 minutes, and preferably has a melt index (I 2 ) in the range of about 0.04 to about 0.2 gram per 10 minutes. It can also have a melt index (I 5 ) of about 0.06 to about 2.5 grams per 10 minutes, and preferably has a melt index (I 5 ) of about 0.2 to about 1.0 gram per 10 minutes.
  • the resin can have a flow index (I 21 ) in the range of about 2 to about 40 grams per 10 minutes, and preferably has a flow index in the range of about 6 to about 20 grams per 10 minutes.
  • Melt index (I 2 ) is determined under ASTM D-1238, Condition E. It is measured at 190° C. and 2.16 kilograms and reported as grams per 10 minutes.
  • Melt index (I 5 ) can be determined under ASTM D-1238, Condition P. It is measured at 190° C. and 5 kilograms and reported as grams per 10 minutes.
  • Flow index (I 21 ) is determined under ASTM D-1238, Condition F. It is measured at 190° C. and 21.6 kilograms, and reported as grams per 10 minutes.
  • Melt flow ratio is the ratio of flow index to melt index.
  • the melt flow ratio (I 21/ I 5 ) of the HDPE can be in the range of about 16 to about 33, and is preferably in the range of about 20 to about 29.
  • the density of the HDPE can be in the range of 0.940 to 0.958 gram per cubic centimeter, and is preferably in the range of 0.943 to 0.953 gram per cubic centimeter.
  • the bis-triarylsilyl chromates and a method for their preparation are described in these patents. Examples of these compounds are bis-triphenylsilyl chromate; bis-tritolylsilyl chromate; bis-trixylylsilyl chromate; bis-trinaphthylsilyl chromate; bis-triethylphenylsilyl chromate; bis-trimethylnaphthylsilyl chromate; and bis-adamantyl chromate.
  • the hydrocarbylaluminum compounds that can be used as co-additives are trihydrocarbylaluminum compounds, hydrocarbylaluminum halides, hydrocarbylaluminum hydrocarbyloxides, and hydrocarbylaluminum hydrides.
  • the hydrocarbyl group can contain from 1 to about 14 carbon atoms, and the halogen can be chlorine, bromine, fluorine, or iodine.
  • the hydrocarbyl group can be an alkyl, aralkyl, aryl, alkaryl, alicyclic, or bicyclic group.
  • hydrocarbylaluminum compounds are trimethylaluminum, triethylaluminum, tributylaluminum, tridecylaluminum, tridodecylaluminum, diethylaluminum chloride, dibutylaluminum chloride, dibutylaluminum bromide, dibutylaluminum iodide, dibutylaluminum fluoride, dihexylaluminum chloride, methylaluminum dichloride, ethylaluminum dibromide, butylaluminum dichloride, pentylaluminum dichloride, diethylaluminum hydride, dibutylaluminum hydride, dihexylaluminum hydride, methylaluminum dihydride, ethylaluminum dihydride, butylaluminum dihydride, and pentylaluminum dihydride.
  • R is a hydrocarbyl group as defined above, X is a halogen, a hydrocarbyloxide, or a hydrogen and n is an integer from 1 to 3.
  • hydrocarbylboron compounds that can be used in the practice of this invention are compounds of the general formula
  • R is a hydrocarbyl group having 1 to 14 carbon atoms.
  • examples are trimethylborane, triethylborane, triisobutylborane, and tributylborane.
  • Triethylborane is the preferred modifying agent of this class.
  • hydrocarbylaluminum hydrocarbyloxides which are commonly termed “alkylaluminum alkoxides" are compounds of the general formula
  • n is an integer from 1 to 2
  • R is a hydrocarbyl group having 1 to 14 carbon atoms, preferably 1 to 8 carbon atoms.
  • the hydrocarbyl group can be alkyl, aralkyl, aryl, alkaryl, alicyclic, or bicyclic.
  • Examples are methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, n-pentyl, iso-pentyl, t-pentyl, hexyl, cyclohexyl, 2-methy-pentyl, heptyl, octyl, 2-ethylhexyl, cyclohexylmethyl, nonyl, decyl undecyl, dodecyl, tridecyl, tetradecyl, benzyl, pinyl, pinylmethyl, phenethyl.
  • hydrocarbylaluminum hydrocarbyloxide compound is diethylaluminumethoxide.
  • hydrocarbyl groups, the halide groups, and the hydride groups are independently selected, i.e., these groups can be the same or different.
  • silica is the preferred support, other inorganic oxides can be used.
  • useful support materials are aluminum phosphate, alumina, silica 1 alumina mixtures, silica modified with a hydrocarbylaluminum compound such as triethylaluminum, silica modified with diethylzinc, silica modified with a titanium tetrahydrocarbyloxide compound such as titanium tetraisopropoxide, silica/titania cogels, titanias and a mixture of silica and calcium carbonate.
  • the catalyst can be prepared by reacting the bis-triarylsilyl chromate, the hydrocarbylaluminum compound or hydrocarbyl boron compound, and a dehydrated support material together.
  • the bis-triarylsilyl chromate reacts with hydroxyl groups, which are present on the surface of the support.
  • the chromate is for the most part chemically adsorbed on the surface of the support. Any part of the chromate, which is not chemically adsorbed, is physically adsorbed on the surface of the support. Usually, about 50 to about 100 percent of the chromate is chemically adsorbed. It should be noted, however, that the chromate retains one or more reactive groups, which react with the hydrocarbyl aluminum or boron compound.
  • the amount of support used is generally that which will provide about 0.01 to about 0.3 millimole of chromium per gram of support and preferably about 0.03 to about 0.1 millimole of chromium per gram of support.
  • the polymerization is conducted in the gas phase using a fluidized process. It is preferably carried out in the continuous mode.
  • a typical fluidized bed reactor is described in U.S. Pat. No. 4,482,687.
  • the atomic ratio of aluminum to chromium can be in the range of about 0.1:1 to about 2.9:1, and is preferably in the range of about 1:1 to about 2:1. Most preferred is a ratio of about 1.5:1.
  • the amount of catalyst can be in the range of about 0.005 to about 0.25 parts by weight based on 100 parts by weight of high density polyethylene, and is preferably in the range of about 0.01 to about 0.1 parts by weight.
  • oxygen can be introduced into the reactor in the range of about 0.005 to about 0.5 part by volume per million parts by volume of ethylene feed, and is preferably added in the range of about 0.005 to about 0.25 part by volume per million parts by volume of ethylene feed. The most preferred amount is in the range of about 0.01 to about 0.1 ppmv (part by volume per million parts by volume) of ethylene feed.
  • Oxygen Add-Back is a dilute system of oxygen in nitrogen added to the reactor in a controlled flow relative to the feed rate of ethylene to the reactor to achieve the desired oxygen add-back level in ppmv.
  • other catalyst poisons can be used to produce the same effect.
  • catalyst poisons can be introduced from external sources just as the oxygen or they can be present as impurities in the ethylene feed or other gases or liquids added to the reactor.
  • useful and preferred catalyst poisons in addition to oxygen, are acetone and other oxygen bearing compounds, methanol and other hydroxyl bearing compounds, and water.
  • Various nitrogen, phosphorus, sulfur, arsenic and halogen bearing compounds can also be useful in this respect, but are less commonly encountered as impurities in ethylene feed or other gases or liquids added to the reactor.
  • One of the effects of the catalyst poison is to lower the molecular weight of the polymer. This is reflected in increased melt and flow indices. In any case, oxygen is the preferred catalyst poison.
  • the molar ratio of alpha-olefin to ethylene can be about 0.0001:1 to about 0.1:1, and is preferably about 0.005:1 to about 0.03:1. Most preferred is a molar ratio of about 0.0075:1 to about 0.01:1.
  • the polymerization can be carried out at a temperature in the range of about 80 to about 110 degrees C., and is preferably carried out at a temperature in the range of about 85 to about 100 degrees C. Most preferred is a temperature in the range of about 90 to about 95 degrees C.
  • a relatively low boiling inert hydrocarbon can be introduced into the reactor and passed through the recycle line where it is vaporized when it is introduced upstream of the condenser.
  • the hydrocarbon is introduced in an amount sufficient to raise the dew point temperature of the cycle gas.
  • the cycle gas is partially condensed in the cycle gas cooler, and is recycled to the reactor to promote cooling by evaporation.
  • the hydrocarbon can also be introduced into the recycle gas line downstream from the condenser. This condensing mode technique is discussed in more detail below.
  • the pressure i.e., the total pressure in the reactor, can be in the range of about 250 to about 515 psia (pounds per square inch absolute) and is preferably in the range of about 300 to about 415 psia.
  • the ethylene partial pressure is set as noted above.
  • the balance of the total pressure is provided by alpha-olefin(s) and/or an inert gas such as nitrogen.
  • STY Space/Time/Yield
  • a typical fluidized bed reactor can be described as follows and is also described in U.S. Pat. No. 4,482,687.
  • the bed is usually made up of the same granular resin that is to be produced in the reactor.
  • the bed comprises formed polymer particles, growing polymer particles, and catalyst particles fluidized by polymerization and modifying gaseous components introduced at a flow rate or velocity sufficient to cause the particles to separate and act as a fluid.
  • the fluidizing gas is made up of the initial feed, make-up feed, and cycle (recycle) gas, i.e., alpha-olefins and/or an inert carrier gas, and other reactor gases.
  • cycle gas i.e., alpha-olefins and/or an inert carrier gas, and other reactor gases.
  • a low boiling inert hydrocarbon is also added to the reactor. When added upstream of the cycle gas cooler, it vaporizes and becomes a part of the cycle gas.
  • This hydrocarbon generally boils (normal boiling point at atmospheric pressure) at a temperature in the range of about minus 10 to about plus 100 degrees C.
  • hydrocarbons are isobutane, isopentane, hexane, and heptane. Isopentane and hexane are preferred. Isopentane is introduced into the recycle line in an amount of about 2.5 to about 25 parts by volume per 100 parts by volume of cycle gas. Hexane is introduced in an amount of about 1 to about 10 parts by volume per 100 parts by volume of cycle gas.
  • the essential parts of the reaction system are the vessel, the bed, the gas distribution plate, inlet and outlet piping, a cycle or recycle gas line, a compressor, cycle gas cooler, and a product discharge system.
  • a cycle or recycle gas line In the vessel, above the bed, there is a velocity reduction zone, and, in the bed, a reaction zone. Both are above the gas distribution plate.
  • the inert hydrocarbon enters the recycle line, raises the dew point temperature of the cycle (or recycle) gas, is partially condensed in the cycle gas cooler (condenser) when it is added upstream of the cooler, and then passes into the reactor where, along with other condensed cycle gas, it vaporizes and cools the exothermic polymerization reaction.
  • cyclohexane extractables are about 3 to about 7 percent by weight based on the weight of the HDPE, and is preferably about 4 to about 6 percent by weight. Further, PENT test failure times are found to be at least 50 hours, and preferably greater than 60 hours.
  • the HDPE resin can be extruded into pipe, or other products in a conventional extruder adapted for the particular product desired. Extruders and processes for extrusion are described in U.S. Pat. Nos. 4,814,135; 4,857,600; 5,076,988; and 5,153,382.
  • a typical single screw type extruder can be described as one having a hopper at its upstream end and a die at its downstream end. The hopper feeds into a barrel, which contains a screw. At the downstream end, between the end of the screw and the die, is a screen pack and a breaker plate.
  • additives which can be introduced into HDPE's, are exemplified by antioxidants, ultraviolet absorbers, anti-static agents, pigments, dyes, nucleating agents, fillers, slip agents, fire retardants, plasticizers, processing aids, lubricants, stabilizers, smoke inhibitors, viscosity control agents, and crosslinking agents, catalysts, and boosters, tackifiers, and anti-blocking agents.
  • the additives can be present in the blend in amounts of about 0.05 to about 5 parts by weight of additive for each 100 parts by weight of polymer blend.
  • Fillers can be added in amounts up to 20 parts by weight and more for each 100 parts by weight of the blend.
  • these products contain a primary antioxidant, a secondary antioxidant, and, in many cases, a processing aid.
  • a primary antioxidant is IRGANOXTM 1010
  • an example of a secondary antioxidant is IRGAFOSTM 168.
  • processing aids are calcium stearate, zinc stearate, and fluoroelastomers.
  • a preferred additive system includes IRGANOXTM 1010 and IRGAFOSTM 168 antioxidants. In parts per million by weight, preferred amounts are about 500 to about 2,000 ppmw for each of the primary and secondary antioxidants, and about 200 to about 800 ppmw for the processing aid. The ppmw are based on a million parts by weight of ethylene.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
US08/911,263 1997-08-14 1997-08-14 Process for the preparation of polyethylene Expired - Lifetime US6022933A (en)

Priority Applications (16)

Application Number Priority Date Filing Date Title
US08/911,263 US6022933A (en) 1997-08-14 1997-08-14 Process for the preparation of polyethylene
ZA986046A ZA986046B (en) 1997-08-14 1998-07-08 A process for the preparation of polyethylene
ARP980103910A AR016807A1 (es) 1997-08-14 1998-08-07 Un procedimiento para preparar polietileno.
CN98810070A CN1275136A (zh) 1997-08-14 1998-08-13 聚乙烯的制备方法
CZ20000521A CZ299738B6 (cs) 1997-08-14 1998-08-13 Zpusob výroby vysokohustotního polyethylenu
KR1020007001467A KR20010022865A (ko) 1997-08-14 1998-08-13 폴리에틸렌의 제조 방법
PCT/US1998/016851 WO1999009075A1 (en) 1997-08-14 1998-08-13 A process for the preparation of polyethylene
PL98338556A PL338556A1 (en) 1997-08-14 1998-08-13 Method of obtaining polyethylene
DE69802812T DE69802812T2 (de) 1997-08-14 1998-08-13 Verfahren zur herstellung von polyethylen
ES98940884T ES2165186T3 (es) 1997-08-14 1998-08-13 Procedimiento para la preparacion de polietileno.
PT98940884T PT1003792E (pt) 1997-08-14 1998-08-13 Um processo para a preparacao de polietileno
RU2000106041/04A RU2184743C2 (ru) 1997-08-14 1998-08-13 Способ получения полиэтилена
TR2000/00338T TR200000338T2 (tr) 1997-08-14 1998-08-13 Polietilen'in hazırlanmasına mahsus bir yöntem.
EP98940884A EP1003792B1 (en) 1997-08-14 1998-08-13 A process for the preparation of polyethylene
AT98940884T ATE210157T1 (de) 1997-08-14 1998-08-13 Verfahren zur herstellung von polyethylen
BG104160A BG104160A (en) 1997-08-14 2000-02-16 A process for the preparation of polyethylene

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US08/911,263 US6022933A (en) 1997-08-14 1997-08-14 Process for the preparation of polyethylene

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US6022933A true US6022933A (en) 2000-02-08

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US08/911,263 Expired - Lifetime US6022933A (en) 1997-08-14 1997-08-14 Process for the preparation of polyethylene

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US (1) US6022933A (cs)
EP (1) EP1003792B1 (cs)
KR (1) KR20010022865A (cs)
CN (1) CN1275136A (cs)
AR (1) AR016807A1 (cs)
AT (1) ATE210157T1 (cs)
BG (1) BG104160A (cs)
CZ (1) CZ299738B6 (cs)
DE (1) DE69802812T2 (cs)
ES (1) ES2165186T3 (cs)
PL (1) PL338556A1 (cs)
PT (1) PT1003792E (cs)
RU (1) RU2184743C2 (cs)
TR (1) TR200000338T2 (cs)
WO (1) WO1999009075A1 (cs)
ZA (1) ZA986046B (cs)

Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040186250A1 (en) * 2003-03-21 2004-09-23 Kinnan Michael Allen Methods of polymerizing olefin monomers with mixed catalyst systems
US20040236043A1 (en) * 2001-05-10 2004-11-25 Arild Follestad Olefin polymerisation process
US20050126256A1 (en) * 2003-12-16 2005-06-16 Fina Technology, Inc. Accelerated method to determine or predict failure time in polyethylenes
US20050137365A1 (en) * 2003-12-22 2005-06-23 Mure Cliff R. Blow molding resins with improved escr
US20050267249A1 (en) * 2004-05-06 2005-12-01 Wilson Debra R Polymer molding compositions
US20060155081A1 (en) * 2003-03-28 2006-07-13 Jorgensen Robert J Chromium-based catalysts in mineral oil for production of polyethylene
US20060223958A1 (en) * 2005-03-31 2006-10-05 Fischbuch D B Processes for producing high density polyethylene
US20070027276A1 (en) * 2005-07-27 2007-02-01 Cann Kevin J Blow molding polyethylene resins
US20070078239A1 (en) * 2005-10-04 2007-04-05 Ping Cai Gas-phase polymerization process to achieve a high particle density
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DE69802812T2 (de) 2002-04-04
RU2184743C2 (ru) 2002-07-10
CZ2000521A3 (cs) 2000-07-12
ATE210157T1 (de) 2001-12-15
ES2165186T3 (es) 2002-03-01
CZ299738B6 (cs) 2008-11-05
ZA986046B (en) 1999-02-01
KR20010022865A (ko) 2001-03-26
EP1003792A1 (en) 2000-05-31
AR016807A1 (es) 2001-08-01
PT1003792E (pt) 2002-05-31
EP1003792B1 (en) 2001-12-05
CN1275136A (zh) 2000-11-29
TR200000338T2 (tr) 2000-11-21

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